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8/20/15

LECTURE11:
INDUSTRIAL GASES (H2, N2, O2, CO2,
ACETYLENE, ETC.)

CHEMICAL TECHNOLOGY (CH-206)


Department of Chemical Engineering

ACETYLENE: INTRODUCTION
Acetylene

Properties
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Molecular formula C2H2

IUPAC name: Ethyne


Systematic name: Ethyne

Molar mass

26.04 g mol1

Appearance

Colourless gas

Odour

Odourless gas

Density

1.097 g/L = 1.097 kg/m3

Melting point

80.8C
Triple pointat 1.27 atm

Sublimation
conditions

84 C (1 atm)

Solubility

Acetone, DMF, slightly


soluble in water

Vapor pressure
http://en.wikipedia.org/wiki/Acetylene

44.2 atm (20C)

ACETYLENE: CHARACTERISTICS
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Pure acetylene is odorless, but commercial grades have a


marked odor due to impurities.
It is unstable in pure form, therefore it is usually handled as a
solution (by dissolving in acetone or dimethylformamide
(DMF), contained in a metal cylinder with a porous filling,
asbestos)
It is somewhat poisonous in nature.
It burns with luminous flame and form explosive mixture with
air.
Acetylene can easily react in an addition-type reaction to form
number of products like benzene, vinyl acetylene etc., which
are exothermic reactions and do not require oxygen to proceed.
Acetylene can explode if the absolute pressure of the gas
exceeds about 200kPa (29 psi), therefore, the safe limit for
acetylene is 101 kPag or 15 psig.

ACETYLENE: TIMELINE
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In 1836, Edmund Davy identified acetylene as a


"new carburet of hydrogen".
In 1860, Marcellin Berthelot, named it as
"acetylene.

Berthelot

prepared acetylene by passing vapours of


organic compounds (methanol, ethanol, etc.) through
a red-hot tube and collecting the effluent.
Berthelot also formed acetylene by sparking
electricity through mixed cyanogen [(CN)2] and
hydrogen gases.
Berthelot later obtained acetylene directly by passing
hydrogen between the poles of a carbon arc.

ACETYLENE: APPLICATIONS
For the chemical manufacture of
acrylonitrile,

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vinyl chloride, vinyl acetate, acrylates

etc.
acetaldehyde, trichloroethylene, acetic acid, polyvinyl
alcohol, perchloroethylene etc.
propagryl alcohol, butyrolactone, vinyl pyrrolidine
etc.

In metallurgy industries for welding and cutting


It is also used as a fuel.

ACETYLENE: PROCESSES
2.
3.

Calcium carbide
Paraffin hydrocarbons by pyrolysis (Wulff
process)
Natural gas by partial oxidation (Sachasse
process)

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1.

ACETYLENE:
ACETYLENE FROM CALCIUM
CARBIDE
Raw materials
Basis:

1000 cu ft. acetylene


Calcium carbide (85%)
100kg
Water
815kg

Sources of raw material


Calcium

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carbide is manufactured from lime and coke in


60:40 ratio in electric furnace at 20002100 0C temperature.

Reaction (Friedrich Whler in 1862 )


CaC2 + 2H2O Ca(OH)2 + C2H2
(H = 32.5kcals)7

ACETYLENE:
ACETYLENE FROM CALCIUM
CARBIDE
There are two methods for the acetylene
manufacture from calcium carbide
1.
2.

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Wet process
Dry process

Wet process,
.Calcium

carbide is added to large quantity of water


releasing acetylene gas and calcium hydrate as
residue.
.Calcium hydrate is discharged in the form of lime
slurry containing approximately 90% water.
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ACETYLENE:
ACETYLENE FROM CALCIUM CARBIDE
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Dry Process

Block diagram of manufacturing process

ACETYLENE:
ACETYLENE FROM CALCIUM
CARBIDE
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Process flow diagram for acetylene manufacture

10

Animation:
http://nptel.ac.in/courses/103106108/downloads/swf%20file/Acetylene%20fro
m%20calcium%20carbide.swf

ACETYLENE:
ACETYLENE FROM CALCIUM
CARBIDE
Dry process
Equal

amount of water is added to CaC2 (1:1 ratio) in


a generator, in order to eliminate the waste of
calcium hydrate.
The heat of reaction (~6.2 MJ/m3 of acetylene) is used
to vaporize the excess water over the chemical
equivalent, leaving a substantially dry calcium
hydrate, which is suitable for reuse as a lime source.
Throughout the process, the temperature is
controlled below 150 0C at 15psi (1.03 bar) pressure
because the acetylene
after mixing with air explodes at 4800C,
polymerizes to form benzene at 6000C, and
decomposes at 7800C.

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11

ACETYLENE:
ACETYLENE FROM CALCIUM
CARBIDE
The crude acetylene gas containing traces of H2S,
NH3 and phosphine (PH3) form generator is

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either

scrubbed with water and caustic soda solution


or sent to purifier where the impurities are absorbed
by the use of iron oxide or active chlorine compounds.

The dry gas is fed to cylinders or sent to


manufacturing units.

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ACETYLENE:

PARAFFIN HYDROCARBONS BY PYROLYSIS (WULFF PROCESS)

In the Wulff process acetylene is produced by thermal


decomposition of hydrocarbons such as methane, ethane, propane,
butane, ethylene etc.

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Raw materials
Basis: 1000kg acetylene (100%)
Natural gas
262000 Scf
Steam (600psig)
26308 kg
Electricity 140 kWH
Cooling water 25000 gal
Process water 200 gal
Solvent (make up) 2.95 kg
Reaction
C4H10 C2H2 + C2H4 + CO + H2
C 2 H4 C 2 H2 + H 2
2CH4 C2H2 + 3H2

(H = + 96.7kcals)

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ACETYLENE:

PARAFFIN HYDROCARBONS BY PYROLYSIS (WULFF


PROCESS)
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Block diagram of manufacturing process


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ACETYLENE:

PARAFFIN HYDROCARBONS BY PYROLYSIS (WULFF


PROCESS)
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Manufacture of Acetylene by Wulff Process

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Animation:
http://nptel.ac.in/courses/103106108/downloads/swf%20file/Acetylene%20by%2
0wulff%20process.swf

ACETYLENE:

PARAFFIN HYDROCARBONS BY PYROLYSIS (WULFF PROCESS)


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First, the hydrocarbon feed is diluted with steam (up to 1:8 ratios).
Pyrolysis is performed in a Wulff regenerative furnace, which is a
rectangular steel box filled with refractory bricks checker work.
The feed is carried through the chamber at sub-atmospheric pressure by
virtue of a large vacuum pump, thereby reducing the residence time as
small as 0.03 s.
Cracked gases leaves the chamber at about 370C.
The maximum temperature in the furnace just after the heating cycle
approaches 1315C.
The furnace is operated in four minutes cycle in which the checker work is
first heated for one minute and then feed gas pyrolyzed for one minute.
The same sequence of operation is then done in reverse direction through
the furnace. To facilitate reversal of the gas flow, fuel gas burners and
hydrocarbon feed pipes are located on each side of the combustion chamber.
To allow continuous flow of cracked gases to the purification train, two
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furnaces are usually operated on staggered cycles.

ACETYLENE:

PARAFFIN HYDROCARBONS BY PYROLYSIS (WULFF


PROCESS)
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Cooled cracked gases from the chamber are then


further quenched in a tar trap, where steam and
various tars are removed.
The gas is compressed to atmospheric pressure,
passed through a knock-out forum and electrostatic
precipitator, and sent to the recovery system.
Diacetylene and acetylene are separated by
absorption in DMF (dimethyl formamide).

By

proper adjustment of solvent ratio and temperature,


diacetylene is removed in the first scrubbing column.

In the acetylene absorber small quantities of


ethylene, CO2 and higher acetylenes are also
absorbed.

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ACETYLENE:

PARAFFIN HYDROCARBONS BY PYROLYSIS (WULFF


PROCESS)

volume of off-gas is much more than is required for


fuel, so it may be either recycled to the furnace or used
as a raw material for some other operation.

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Acetylene rich solution is sent to stabilizer, where


less soluble components are removed by stripping.
Acetylene is then removed from the solvent in a
second stripping column.
The solvent is regenerated for reuse by stripping
out high boilers by blowing with off gas from the
acetylene absorber-followed by rectification.
The acetylene free off-gases (ethylene, carbon
monoxide, hydrogen and methane) are used as fuel
for heating the combustion chamber.

The

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ACETYLENE:

PARAFFIN HYDROCARBONS BY PYROLYSIS (WULFF


PROCESS)
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Yield of acetylene (98.5 to 99.3 % purity) varies


with the hydrocarbon feed stock used.
Average yields for the once-through process are:

22.5

kg per 100kg methane,


38.6 kg per 100kg ethane, and
35.5kg per 100kg propane.

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ACETYLENE:

NATURAL GAS BY PARTIAL OXIDATION (SACHASSE


PROCESS)

Acetylene may be produced from a variety of hydrocarbon feed stocks


(natural gas, LPG, naphtha, fuel oil, even crude oil) by high-temperature
cracking.

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Raw materials
Basis:

1000kg acetylene (99.5%) plus 340000 Cu ft. off gas (345 Btu/Cu ft.)
Natural gas
190000 Sef
Oxygen (95%) 5400 kg
Solvent
2.3 kg
Power 15000 kWH
Steam 4535.9 kg
Cooling water 22710 liter

Reaction
CH4 + 2O2 CO2 + 2H2O
2CH4 C2H2 + 3H2

(H = + 79.8 kcals)

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ACETYLENE:

NATURAL GAS BY PARTIAL OXIDATION (SACHASSE PROCESS)


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Block diagram of manufacturing process


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ACETYLENE:

NATURAL GAS BY PARTIAL OXIDATION (SACHASSE PROCESS)


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Diagram with process equipment


Animation:
http://nptel.ac.in/courses/103106108/downloads/swf%20file/Acetylene.swf

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ACETYLENE:

NATURAL GAS BY PARTIAL OXIDATION (SACHASSE


PROCESS)
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Natural gas (1 mole) and low purity oxygen (0.65 moles


95%O2) are preheated separately to 510 0C and fed to a
specially designed burner.
The converter is vertical cylindrical unit built in three
sections

Mixing chamber
Flame room
Quench chamber

After rapid and uniform mixing of O2 and CH4 in the mixing


chamber, the gases are fed to the flame room through the
portal in a burner block designed to prevent back travel or
blow-off.
The heat of combustion heats the gases to 1550 0C to allow
cracking of the excess methane to acetylene.
The residence time is 0.001 to 0.01 seconds.

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ACETYLENE:

NATURAL GAS BY PARTIAL OXIDATION (SACHASSE


PROCESS)

These gases are run to a filter where using


carbon black, acetylene of 99.5% or higher purity
is produced (23.5kg/1000kg of acetylene is
separated and purified in a manner as described
for the Wulff process).

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The decomposition of acetylene is prevented by


rapid quenching of the resulting gases with water
to 38 0C.
The cooled effluent gases on the dry basis contain
8% acetylene, 54% H2, 26% CO, 5% CH4, 4% CO2
and 3% N2 and higher acetylenes.

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CARBON DIOXIDE

INDUSTRIAL GASES: CARBON


DIOXIDE
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Carbon dioxide (CO2) is composed of two oxygen


atoms covalently bonded to a single carbon atom.
It is a trace gas with a concentration of 0.039% by
volume in atmospheric air.

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CARBON DIOXIDE
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In 7th century, Jan Baptist Van Helmont observed that during burning
of charcoal in the closed vessel, the mass of the resulting ash was
much less than that of the original charcoal.
In 1750 Joseph Black studied the Carbon dioxides properties by
treating limestone with acids to yield a gas (fixed air).

He

observed that gas was denser than air and supported neither flame nor
animal life.
when the gas is bubbled through an aqueous solution of lime, it would
precipitate calcium carbonate.

Joseph Priestley, in 1772 invented the soda water preparation by


dripping sulfuric acid on chalk in order to produce CO 2, and forcing the
gas to dissolve by agitating a bowl of water in contact with the gas.
Humphry Davy and Michael Faraday first liquefied CO 2 at elevated
pressure in 1823.
In 1834 Charles Thilorier solidifies CO 2, in pressurized container of
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liquid CO2 .

CARBON DIOXIDE: PROPERTIES


Molecular formula :

CO2

Molecular weight
: 44.01gm/mole
Appearance
: Colourless gas
Odour
: Odourless gas
Boiling point
: 57 0C
Melting point
: 78 0C
Density (1 atm and 00C): 1.977 kg/m3
Solubility
:
Soluble in water

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CARBON DIOXIDE: APPLICATIONS


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Refrigeration process (dry ice)


Carbonated process in liquid CO form.
2

Used in creating inert atmosphere.


As fire extinguisher
Gaseous CO used as a neutralizing agent
2

Gaseous CO2 is the basic raw material for


production of Na2CO3, NaHCO3

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CARBON DIOXIDE: SOURCES

By burning of carbonaceous materials


C + O2 CO2 (10 to 18% Pure) H = 23.16kcals

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In the production of H2 by steam water gas 16% pure CO2


is obtained.
In manufacture of alcohol (ethanol) by the fermentation
process. 99.9 % pure CO2 is obtained.
In calcinations of CaCO3, 40% CO2 is obtained 1000 C
CaCO3 CaO + CO2 (40%)

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CARBON DIOXIDE: MANUFACTURE

Raw materials
Coke or coal
Air

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Reaction
C + O2 CO2 (10 to 18% Pure) H = 23.16 kcals
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CARBON DIOXIDE: PROCESS


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Block diagram for CO2 synthesis

32

CARBON DIOXIDE: PROCESS


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345 0C

Process flow diagram for CO2 synthesis

33

CARBON DIOXIDE: CO2 RECOVERY


Ethanolamine process
Sodium carbonate process
Potassium carbonate process
1. In all the process CO2 is recovered by absorptiondesorption.
2. The CO2-bearing gases are passed in counter-current
manner to a solution that removes the CO2 by
absorption and retains it until desorbed by heat in a
separate piece of equipment.
3. Due to relatively low water solubility of CO2, water
alone is not used as a absorption medium.
4. Alkali carbonate and ethanolamine solutions are used
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due to the higher solubility of CO2 with the absorbing
medium.

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GIRBOTOL AMINE PROCESS


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It was developed by the Girdler Corporation of


Louisville, Kentucky.
The process uses aqueous solutions of an mono-,
di- or triethanolamine as absorption medium.

2OHC2H4NH2 + H2O + CO2 (OHC2H4NH3)2CO3

35

GIRBOTOL AMINE PROCESS


Forward reaction proceeds at low temperatures (65 0C) and absorbs
CO2 from the gas in the absorber.

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The amine solution, rich in CO2, passes out of the bottom of the
tower and through heat exchanger, where it is preheated by hot,
lean solution returning from the re-activator.
Then solution passes countercurrent to a stream of CO 2 and
steam, which strips CO2 out of the solution.

As the solution reaches to bottom of the tower, where heat is


supplied by a steam heated or direct fired re-boiler, it has been
reactivated.
This hot solution (1400C) passes out of the tower, through the heat
exchanger and cooler, and returns to the absorber tower.
In the case of flue gases containing oxygen, small side stream of
solution is passed through re-distillation unit, where the oxidation
products are removed and the distilled amine is returned to the
process.

36

GIRBOTOL AMINE PROCESS


Advantages
Complete

removal of carbon dioxide


Regeneration up to 100% with moderate steam
consumption is possible
Higher absorption of CO2 in the solution
Lower

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operating cost

37

SODIUM CARBONATE PROCESS


Recovery of pure carbon dioxide from gases containing other diluents, such as
nitrogen and carbon monoxide, is based on the reversibility of the above reaction.
This reaction proceeds to the right at low temperatures and takes place in the
absorber where the CO2 bearing gases are passed countercurrent to sodium
carbonate solution.

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Na2CO3 + H2O + CO2 2NaHCO3

CO2 absorption rate depends up on temperature, pressure, partial pressure of CO 2 in the


gas, and solution strength.

Reverse reaction will proceed when heat is applied and is carried out in lye boiler.
A heat exchanger serves to preheat the strong lye as it approaches the boiler and
cool the weak lye returning to the absorber.
Additional weak lye cooling is accomplished in lye cooler to permit the reaction to
proceed further to the right in the absorber.
CO2 gas and water vapour released from the solution in the boiler pass through
steam condenser where the water condenses out and returns to the system.
The cool CO2 proceeds to the gas holder and compressors.

38

POTASSIUM CARBONATE
PROCESS
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The process is similar to sodium carbonate


process, however potassium bicarbonate has more
solubility than its corresponding sodium salt, it
provides better absorption of CO2 than other
process.
This process used for removing CO from NH
2
3
synthesis gas mixtures, and from natural gas.

39

POTASSIUM CARBONATE
PROCESS

The solution sends to the CO2 stripping tower operating at or


near atmospheric pressure.
Part of the absorbed CO2 flashes out of the solution as it
enters the stripping tower, and the balance is stripped from
the solution by steam.
The overall energy requirements for CO 2 recovery by the hot
carbonate process are lower than for other processes when the
gases being scrubbed have high carbon dioxide partial
pressures.

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Absorbent solution flows directly from the lye boiler to the


absorber without cooling.
The gas streams are treated at 250 psig, or higher pressure
which increases the partial pressure of CO 2 so that the hot
K2CO3 solution (20-30%) will absorb substantial amount of
CO2 at 1100C.

40

CARBON DIOXIDE: PURIFICATION


Carbon dioxide obtained can be further purified
by the following two process.
Purification
Purification

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of low % CO2 containing gas.

of high % CO2 containing gas.

41

CARBON DIOXIDE:
PURIFICATION OF LOW % CO2 CONTAINING GAS
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Hot CO2 gas, with low concentration (18%), passes through a heat
exchanger to lower the temperature.
It is then scrubbed with water to remove SO2 and dust particles.
The gas is further scrubbed in packed towers where, it is scrubbed
with Na2CO3 solution and absorbed in it to form NaHCO3 solution in
second tower.
Solution is heated in heat exchanger to remove absorbed CO2. ,
which is further cooled in cooler and stored.

42

CARBON DIOXIDE:
PURIFICATION OF LOW % CO2 CONTAINING GAS
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43

CARBON DIOXIDE:
PURIFICATION OF HIGH % CO2 CONTAINING GAS
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Gases are first compressed to 80psi pressure and passes through a


scrubber to remove organic matters with KMnO4.
The gas is then dehydrated using silica gel or activated alumina or conc.
H2SO4 by passing through dehydration tower.
The gas is then scrubbed with oil to remove bad odour of gas.
Now the gas is, compressed in two stages, 80 psi to 300 psi and 300 psi to
900 psi for getting compressed gas or liquid, respectively.
For liquid CO2 the temperature is brought down much below 31.1 C.
After compression by cooling of CO2, the liquid is stored at 10 C
44
temperature.
If the liquid CO2 is passes through an expansion tank and pressure is
released then the solid CO2 is formed at 40 C temperature.

CARBON DIOXIDE:
PURIFICATION OF HIGH % CO2 CONTAINING GAS
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45

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INDUSTRIAL GASES: O2 AND


N2
46

OXYGEN (O2) AND NITROGEN (N2)


Composition of air:
Wt% in air

Nitrogen (N2)

78.01

Oxygen (O2)

20.99

Carbon dioxide (CO2)

0.03 0.07

Argon (Ar)

0.94

Hydrogen (H2)

0.01

Neon (Ne)

0.0015

Exceptand
CO2Krypton
the concentration
of all0.01
the gases
Helium
(He and Kr)
0.02 listed above are
present in air are constant.
Also, water vapours and traces of ozone and iodine are present in
air in variable amounts.
The composition of air also depends on altitude and distance to
sea, in neighbourhood of industry, built up urban areas, nearby
volcanic phenomena.
Other gases such as CO, H2S and NO2 are also present in air.

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Gas

47

OXYGEN (O2) AND NITROGEN (N2)


Some important facts about gases:
According

to kinetic theory a gas consists of swiftly


moving molecules moving in random manner.
During the movement some molecules collide with
one another, and some repel others, these phenomena
leaving an average distance between the molecules.
At lower pressure the average distance is large, and
at high pressure the molecules are brought near to
one another.
If the temperature increases the repulsion between
the molecules increases, i.e. the volume increases.
If temperature decreases the attraction between the
molecules increases.

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48

CRITICAL TEMPERATURE AND


PRESSURE
Critical temperature
When

the distance between the molecules decreases and molecules


come close to each other, the gas assumes the liquid form provided
the repulsive tendency has been diminished beyond a certain point
known as critical temperature, which is different for different
gases.
The temperature below which any gas can be liquefied by increasing
the pressure.
Above the critical temperature any gas cannot be liquefied by
compression.

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Critical pressure
The

minimum pressure under which gas liquefies at the critical


temperature is called as critical pressure.
Therefore, for cooling purpose, the air should be cooled at very high
pressure and low temperature.
The liquid form is obtained when the kinetic energy and the
potential energy of the substance is approximately equal.

49

AIR: CRITICAL PROPERTIES OF


GASES
Gases

No.

Critical Temperature

Critical Pressure

(0C)

(atm)

1.

Ethylene

+9.5

50.65

2.

Methane

82.85

45.6

3.

Nitrogen

147.13

33.49

4.

Hydrogen

239.9

12.8

5.

Oxygen

118.75

49.7

6.

Acetylene

+35.5

61.55

7.

Ammonia

+132.5

112.3

8.

Carbon monoxide

138.7

34.6

9.

Carbon dioxide

+31.3

72.9

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Sr.

50

AIR

LIQUEFICATION OF AIR BY JOULE THOMPSON


EFFECT

The change in temperature of a gas or liquid when it is forced


through a valve or porous plug while kept insulated so that no heat
is exchanged with the environment.

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At room temperature, all gases except hydrogen, helium and neon


cool upon expansion by the JouleThomson process.

Outer coil

Inner coil

51

AIR

LIQUEFICATION OF AIR BY JOULE THOMPSON


EFFECT
CO2 free air is compressed to 200 atm and is cooled by water.

The condensed water is removed by passing through


activated alumina.
The compressed air is passed through inner coil of heat
exchangers.
The valve with nozzle is provided at the end of the inner coil.
The gas is allowed to suddenly expand by opening the valve,
which result in decrease of temperature of air.
After expanding the cold air goes out through the outer coil,
is then recompressed to 200 atm pressure, cooled by water
and then again allowed to transverse the inner coil.
The temperature of the incoming air further falls due to the
presence of cold air in the outer coil.

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52

AIR

LIQUEFICATION OF AIR BY JOULE THOMPSON


EFFECT
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Now as the cooled air suddenly expands through the nozzle, the
air suffers cooling, the temperature becomes lower than in the
first operation.
The colder air now passes through the outer coil producing an
atmosphere of lower temperature.
Hence when the cooled compressed air passes repeatedly through
the inner coil and subsequently undergoes Joule-Thomson effect,
the temperature of the air further drops.
In this way progressive cooling takes place until the temperature
of air falls below the critical temperature of oxygen and nitrogen.
During this process, the air undergoes liquefaction in the inner
coil, so on opening the valve liquid air falls in the container.
A part of liquid air evaporates, through the outer coil,
maintaining the low temperature below the critical temperature. 53

LINDES PROCESS (O2 AND N2) (1906)


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Block diagram for Lindes process

54
Process diagram for Lindes process

LINDES PROCESS

The column feed is liquefied air at


200 atm pressure introduced at the
bottom of the column.
Since the boiling point of O 2 (183OC)
and N2 (195OC) are very low, column
does not require any external
heating.
Distillation take place only due to
release of vacuum.

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The distillation tower is specially


designed bubble cap tray double
columns arranged one above another.
The two distillation columns are
having intermediate distillation
dome for effective separation of liquid
enriched with O2.

55

LINDES PROCESS

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Thus a number of recycling from lower


column to upper column and lower
column to dome is required.
The construction of dome includes
number of internal pipes so that
distillate of the lower column collides to
the roof and is returned back to the
column as reflux.
The compressed air, which arrives from
the first section of the plant, acts as the
heating fluid in the heater at the base of
the enrichment column.
The same air, always contained within a
tube, passes out from the lower column
of the tower only to re-enter it higher up
after the pressure to which it is
subjected is reduced by means of a
valve, resulting in the lowering of its
temperature.

56

LINDES PROCESS
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Nitrogen with a small oxygen


impurity collects at the top of
the enrichment column.
After expansion to
atmospheric pressure; this
nitrogen is sent to back as the
reflux in the rectification
column situated above.
The liquid which collects in
the heater at the base of the
enrichment column is fed,
after expansion to atmospheric
pressure onto a suitable plate
of the rectification column.

57

LINDES PROCESS
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Only after number of recycling,


liquid with 82% concentration
of O2 is taken in outer part of
dome.
This liquid goes to further
rectification in upper column
where it is refluxed with N2 rich
liquid coming from lower
column.
The final separation in the
upper column takes place which
has less number of trays.
Gaseous N2 is the top product of
the column and the bottom
product is liquid O2.

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CLAUDE PROCESS
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In 1912, Claude rectified Lindes process by combined


effect of internal and external work in cooling the air to
liquefaction point.
The progressive cooling of compressed air is done by
external work and JouleThomson effect, i.e.

70%

of air is cooled by external work, and


30% by JouleThomson effect

A fraction of gases is expanded in a high speed expander.


If appreciable amount of liquid are allowed to form in the
expander, the efficiency of the expansion process
decreases due to irreversibilities.
Therefore final liquefaction is done by a Joule Thomson
effect.

59

RAW MATERIALS AND PROCESSES


(O2 AND N2)
Raw Materials:
Basis

1 ton of 95% oxygen in 300 tons/day plant


Air 3600 Nm3
Steam 1.75 tons
Cooling water 5 tons
Electricity 450 480 KWH
Plant capacity 50 500 tons/day

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Processes
Linde

refrigeration by JouleThomson effect


Claude refrigeration by adiabatic expansion of
compressed air in a turbo-reciprocating or rotating
expansion machine

60

LINDE FRANKL CYCLE (N2 AS A PRODUCT)

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61

HIGH PURITY OXYGEN (KELLOG LOW PROCESS CYCLE)

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62

PROPERTIES OF O2 AND N2

Molecular formula : O2
Molecular weight : 32gm/mole

Appearance : Colourless gas

Odour : Odourless

Boiling point : 182.950C

Melting point : 218.790C

Nitrogen

Molecular formula : N2

Molecular weight : 28gm/mole

Appearance : Colourless gas

Odour : Odourless gas

Boiling point : 195.790C

Density : 1.429 gm/L


(00C,101.325kPa)
Solubility : Sparingly soluble in
water

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Oxygen

Melting point : 2100C

Density : 1.251gm/L
(00C,101.325kPa)

Solubility : Slightly soluble in


water
63

O2 AND N2 APPLICATIONS
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Oxygen
It is used to produce
oxyacetylene flame to
cutting and welding the
metals
In L.D. process for steel
production
For artificial respiration
in case of patients
For mountain climbers
and high attitude aero
planes flights

Nitrogen

In manufacture of synthetic ammonia, nitric


acid

In manufacture organic nitrates like


propellants and explosives,

Synthetically produced nitrates are key


ingredients of industrial fertilizers

In producing nitrogen oxide.

Applied to create inert atmosphere.

64

ACKNOWLEDGEMENT
Slides are developed from the following references:
Austin

G. T., "Shreves Chemical Process Industries",


Fifth edition, Tata McGraw Hill, NY.
Kent J.A., "Riegel's Handbook of Industrial
Chemistry, CBS Publishers.
Gopala Rao M. & Marshall Sittig, "Drydens Outlines of
Chemical Technology for the 21st Century", Affiliated
East West Press, New Delhi.
Mall I. D., "Petrochemical Process Technology",
Macmillan India Ltd., New Delhi.
http://nptel.ac.in/courses/103106108/Lecture%207.pdf
(Acetylene)
http://nptel.ac.in/courses/103106108/24

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